Numerous polymers of olefins, especially polymers of cycloolefins, produced through metathesis polymerization reactions using a metathesis catalyst are technologically and commercially important materials. Especially important are polymers of cycloolefins that are produced through Ring Opening Metathesis Polymerization (ROMP) reactions. Many such materials are tough and rigid, and have excellent chemical resistance. However, for many high performance applications, even higher stiffness and strength are desirable. In such applications, it is desirable to provide for reinforcement of the polyolefin structure.
Fiber reinforced polymer structures, generally, are known in the polymer art. Fiber reinforcement of polymers such as poly-dicyclopentadiene or other polymers of strained ring cycloolefins has been taught by Leach in U.S. Pat. No. 4,708,969. Improving the physical properties of a glass composite polydicyclopentadiene by heat treatment is taught by Silver in U.S. Pat. No. 4,902,560. A reinforced norbornene polymer matrix including a glass mat reinforcement is taught by Sugawara et al. in U.S. Pat. No. 5,063,103.
However, it has been a problem to provide for a good interface or good adhesion between the reinforcement materials and polyolefins produced through metathesis polymerization reactions. Due to the poor interface between the reinforcement material and the polyolefin, stiffness and strength are lost. Additionally, if such composite materials are exposed to fluids during use, the fluids "wick" along the surface of the reinforcement material, due to the poor adhesion, and eventually wet the entire reinforcement material. The presence of a fluid further adversely affects the adherence of the polyolefin to the reinforcement material, and causes further loss of stiffness and strength. The wicking can cause the resulting composite material to be permeable to liquid, making it not feasible for use with liquids.
Coupling agents, also referred to as sizing agents, are generally known in the polymer art to improve adhesion between reinforcement materials and polymer matrixes. However, it is known that coupling agents, and other impurities, adversely affect traditional metathesis catalysts, and are not usable with such catalysts. Silver U.S. Pat. No. 4,902,560, specifically teaches that in dealing with a metathesis produced reinforced polymer matrix, the reinforcing agent should be "substantially completely free of surface coatings" and that "physical properties of structures prepared with glass containing surface treatments such as, e.g., coupling or sizing agents, deteriorate upon post-cure . . . " See U.S. Pat. No. 4,902,560, Column 3, Lines 51-58.
Sugawara, et al. U.S. Pat. No. 5,063,103, teaches a method of coating a sized glass reinforcement mat with a hydrocarbon. A norbornene polymer is then polymerized with a metathesis catalyst system in the presence of the hydrocarbon coated glass mat to form a reinforced polymer structure. However, the metathesis catalyst never comes into contact with the sizing agent. The hydrocarbon binder layer covers the sizing agent such that it does not adversely affect the metathesis catalyst. The additional step of coating the sized glass mat prior to exposing it to the catalyst is expensive, time consuming, and burdensome.
It is desirable to provide a reinforced composite of a metathesis polymerized olefin polymer, especially a ROMP reaction polymerized cycloolefin polymer, and a process for making the same, wherein the polymer is polymerized with a metathesis catalyst in the presence of a reinforcing material having a coupling agent thereon, and the coupling agent provides for an improved interface between the polymer and the reinforcing material without significantly adversely affecting the polymerization reaction.